The role of coordinating anions in the supporting electrolyte during the electrocatalytic oxidation of glycerol on Pt electrodes

This research explores the glycerol electrooxidation reaction (GEOR) on a platinum electrode, with a special emphasis on the role of the chemical properties of the anion present in the electrolyte composition. Essential knowledge of the mechanism and dynamics of glycerol electrooxidation is obtained through comprehensive studies that involve in situ FTIR measurements and the analysis of electrochemically oscillatory responses. This study addresses on the complex interplay between anion adsorption strength and the GEOR, focusing on the differences in CO adsorption coverage, which is the main strongly adsorbed intermediate. The anion adsorption strength, with the order HClO4 < H2SO4 < H3PO4, affects significantly not only the CO coverage on the platinum surface but also the overall glycerol electrooxidation rate. The observed differences in the electroactivity are attributed to competitive adsorption phenomena, in which specific coordinated ions have greater adsorption capabilities than perchlorate ions. These findings highlight the critical relevance of designing and optimizing electrocatalysts for glycerol electrooxidation and related processes with careful consideration of the electrolyte composition, notably the anion.